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US6787062B2 - Producing liquid crystals with CF2O bond - Google Patents

Producing liquid crystals with CF2O bond Download PDF

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Publication number
US6787062B2
US6787062B2 US10/220,428 US22042802A US6787062B2 US 6787062 B2 US6787062 B2 US 6787062B2 US 22042802 A US22042802 A US 22042802A US 6787062 B2 US6787062 B2 US 6787062B2
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bridge
alkylthio
bis
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US20030069433A1 (en
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Peer Kirsch
Andreas Taugerbeck
Detlef Pauluth
Matthias Bremer
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Merck Patent GmbH
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Merck Patent GmbH
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Priority claimed from DE2000110537 external-priority patent/DE10010537A1/de
Priority claimed from DE10027102A external-priority patent/DE10027102A1/de
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/04—Formation or introduction of functional groups containing oxygen of ether, acetal or ketal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition

Definitions

  • the invention relates to a process for the preparation of compounds having at least one —CF 2 O— bridge in the molecule.
  • Liquid crystals have been widely used ever since the first commercially useful liquid-crystalline compounds were discovered about 30 years ago.
  • Typical application areas are in particular displays for watches and clocks or pocket calculators, or large display panels as used in railway stations, airports or sports arenas.
  • Other application areas are displays of portable computers or navigation systems, and video applications. The latter applications in particular have to meet high requirements on switching times and image contrast.
  • the liquid-crystalline molecules must have certain properties to be useful for commercial applications. To be able to use devices having a liquid-crystal display under various climatic conditions, the molecules must form a stable nematic phase over a very wide temperature range including the room temperature range. The compounds must therefore have a low melting point and a high clearing point.
  • the molecules must have a low rotational viscosity. For example, switching times of less than 16.7 ms are required for video applications.
  • the liquid-crystalline molecules should furthermore have a high dielectric anisotropy so that only low threshold voltages are required. This means that little energy is required so that it is possible to use smaller and lighter accumulators, for example in laptops.
  • Another important factor for the design of the display are the birefringence properties of the molecules which have an effect on contrast and available viewing angle.
  • mixtures which often comprise 5 to 15 different components are employed rather than pure substances. This means that the individual components have to be compatible with one another, i.e. are sufficiently soluble in one another, for example.
  • liquid-crystalline compounds must therefore have a high resistivity and a high voltage holding ratio.
  • Liquid-crystalline compounds which have been found to have a particularly high resistivity are those which contain fluorine-containing groups in their molecular framework.
  • EP 0 844 229 A1 describes liquid-crystalline compounds which contain an —O—CF 2 — bridge.
  • Various methods for obtaining this —O—CF 2 — bridge are suggested.
  • One of the methods described involves initially converting an aromatic halide into a Grignard compound or a lithiated compound followed by conversion into the the dithiocarboxylic acid by means of carbon disulfide.
  • the dithiocarboxylic acid is then converted into a thioester using a phenol in the presence of an alkali metal hydride and iodine.
  • the desired —O—CF 2 — bridge is then formed from the thioester using a fluorinating agent.
  • Another method which is suggested involves initially reacting a cyclohexanone with tris(dimethylamino) phosphine and dibromodifluoromethane to obtain a difluoromethylenehexylidene.
  • a —CF 2 —O— bridge is then formed by addition of bromine to this derivative followed by etherification by reacting with a phenolate with simultaneous elimination of hydrogen bromide.
  • This object is achieved by the process according to the invention, which comprises initially reacting a bis(alkylthio)carbenium salt with a compound containing at least one hydroxyl group in the presence of a base followed by oxidative fluorination, preferably in situ, with a fluorinating agent and an oxidizing agent to form the compound having at least one —CF 2 O— bridge in the molecule.
  • the bis(alkylthio)carbenium salts can be prepared very easily from the corresponding carboxylic acids or activated carboxylic acid derivatives.
  • suitable carboxylic acid derivatives include carbonyl halides, carbonyl pseudohalides, suitably substituted carbonyl sulfonylates, such as a trifluoromethylsulfonylate.
  • carboxylic anhydrides and alkyl- or phenylcarboxylic esters can be used. The salts precipitate in clean form from the reaction solution and can be employed in the next stage without further purification.
  • the bis(alkylthio)carbenium salt is initially reacted with the compound containing at least one hydroxyl group to produce a dithioorthoester.
  • This dithioorthoester is generally not isolated, but immediately reacted further.
  • the oxidative fluorination to form the compound having a —CF 2 O— group is conducted under very mild, slightly basic conditions and is therefore compatible with numerous unprotected functional groups, for example a nitrile group, in contrast to the conventional methods.
  • Another advantage is that the stereochemistry of the radicals, for example a cis-oder trans-cyclohexylene radical, is retained in the reaction.
  • FIG. 1 The principal steps are summarized in FIG. 1 below.
  • FIG. 1 Reaction scheme for the preparation of compounds having a CF 2 O bridge.
  • the carboxylic acid derivative A in which X is, for example, —OH, halogen, pseudohalogen, substituted sulfonate, an anhydride, alkoxy or phenoxy, is then reacted with an alkylthiol to give the bis(alkylthio)carbenium salt B.
  • X is, for example, —OH, halogen, pseudohalogen, substituted sulfonate, an anhydride, alkoxy or phenoxy
  • an alkylthiol Preference is given to using dithiols which lead to the formation of a cyclic cation.
  • Particularly suitable thiols are therefore ethanedithiol, propanedithiol or 1,2-benzenedithiol which lead to the formation of dithianylium and dithiolanylium salts, respectively.
  • R a and R b independently of one another, can be an alkyl, aryl, cycloalkyl or alkenyl radical, where these radicals in turn may be substituted as desired, for example by halogen, pseudohalogen, hydroxyl or carbonyl groups.
  • the bis(alkylthio)-carbenium salt has a structure of the formula I.
  • halogen in particular fluorine, pseudohalogen, —OCF 3 or —OCHF 2 ,
  • R 1 is a linear or branched alkyl or alkoxy radical having 1 to 12 carbon atoms which is unsubstituted, monosubstituted by —CN or —CF 3 or at least monosubstituted by halogen, a linear or branched oxyalkyl, alkenyl or alkenyloxy radical having 2 to 12 carbon atoms or a linear or branched oxalkenyl radical having 3 to 12 carbon atoms, where, in addition, one or more CH 2 groups in these radicals may, in each case independently of one another, be replaced by —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that heteroatoms are not linked directly to one another, or halogen, preferably F or Cl,
  • Z is, in each case independently of one another, a single bond, a —CH 2 —CH 2 —, —CF 2 —CF 2 —, —CF 2 —CH 2 —, —CH 2 —CF 2 —, —O—CO—, —CF ⁇ CF—, —CH ⁇ CH—, —C ⁇ C—, —CO—O—, —O—CO—, —CF 2 —O— or —O—CF 2 — group,
  • —S—(CR 2 R 3 ) n —S— is a bridge consisting of two sulfur atoms which are linked by a carbon chain having two or three carbon atoms, where the hydrocarbon bridge may also carry one or more substituents R 2 and R 3 , in particular alkyl or alkylene groups, where, in addition, the radicals R 2 and R 3 may together form a cycloalkyl group or aryl group,
  • n is 2 or 3
  • Y ⁇ is any desired anion.
  • the process according to the invention is generally suitable for the preparation of compounds having a —CF 2 —O— bridge, such as liquid crystals, intermediates for polymers, pharmaceuticals and crop protection agents, for example. However, it is particularly suitable for the preparation of liquid-crystalline compounds.
  • the radicals R 1 are preferably structural elements customary in liquid-crystalline compounds. Some fragments of this type are listed by way of example in FIG. 2, this list not being exhaustive. R is as defined for R 1 above.
  • FIG. 2 Examples of building blocks customary in liquid-crystalline compounds.
  • the compound containing at least one hydroxyl group is preferably a phenol which may optionally be substituted, and in particular carries a polar group, preferably —F, —Cl, —CN, —NCS, —OCF 3 or —OCH 2 F, or an alkyl, cycloalkyl or phenyl radical in 4-position, which radicals in turn may be substituted by alkyl, cycloalkyl or phenyl radicals, where, in addition, hydrogen atoms may also be substituted by fluorine or chlorine atoms and in each case a —CH 2 —CH 2 —, —CF 2 —CF 2 —, —CF 2 —CH 2 —, —CH 2 —CF 2 —, —CF ⁇ CF—, —CH ⁇ CH—, —C ⁇ C—, —COO—, —O—CO—, —O—CF 2 — or —CF 2 —O— group may be present between these groups.
  • the structure of the compound containing at least one hydroxyl group is not subject to any particular restrictions per se.
  • the radical present in the compound containing at least one hydroxyl group preferably contains structural elements customary in liquid crystals. Examples of structural elements which may be mentioned are again the building blocks depicted in FIG. 2.
  • the bis(alkylthio)carbenium salt preferably contains a noncoordinating or weakly coordinating anion, in particular selected from the group consisting of tetrafluoroborate, hexafluorophosphate, perchlorate and perfluoroalkylsulfonate, in particular trifluoromethanesulfonate. Owing to their very low hygroscopicity, these salts are easy to process.
  • the oxidizing agent used can be any customary oxidizing agent.
  • the oxidizing agent used is preferably a compound which releases halonium equivalents.
  • oxidizing agents are N-bromosuccinimide, N-iodosuccinimide, 1,3-dibromo-5,5-dimethylhydanthoin and bromine. Particular preference is given to bromine, since the resulting bromides are easy to remove.
  • suitable oxidizing agents are SO 2 Cl 2 , SO 2 ClF, nitrosonium and nitronium salts and Chloramin T.
  • the fluorinating agent used can be any customary fluorinating agent.
  • the fluorinating agent is particular preferably selected from the group consisting of aliphatic and aromatic amine/hydrogen fluoride complexes, for example pyridine/hydrogen fluoride complexes, NEt 3 ⁇ 3HF, 50% HF in pyridine, melamine-HF and polyvinylpyridine-HF.
  • the process according to the invention is particularly suitable for the preparation of liquid crystals.
  • the process according to the invention utilizes bis(alkylthio)carbenium salts as starting materials.
  • the invention therefore also relates to bis(alkylthio)carbenium salts of the formula I.
  • Z, —S—(CR 2 R 3 ) n —S—, m, n and Y ⁇ are as defined above.
  • the invention furthermore relates to dithioorthoesters of the formula II
  • R 4 is as defined for R 1 in claim 2, and, in addition, may be —H, —F, —Cl, —CN, —SCN, —OCF 3 or —OCHF 2 , and o is an integer between 0 and 6.
  • reaction mixture was stirred at ⁇ 70° C. for another 90 minutes and then warmed to room temperature.
  • the solution was poured onto saturated sodium hydrogencarbonate solution with stirring, the organic phase was separated and the aqueous phase was extracted twice with dichloromethane.
  • the combined organic phases were dried and the solvent was removed in vacuo. Filtration through silica gel yielded a colourless oil which slowly crystallized.
  • reaction mixture was stirred for another 60 minutes at ⁇ 70° C. and then warmed to room temperature.
  • the solution was poured onto sodium hydrogencarbonate solution, the organic phase was separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried and the solvent was removed. Filtration through silica gel yielded a colourless oil.
  • reaction mixture was stirred for another 60 minutes and then warmed to room temperature.
  • the mixture was poured onto sodium hydrogen-carbonate solution, the organic phase was separated and the aqueous phase was extracted with dichloromethane.
  • the combined organic phases were dried and the solvent was removed in vacuo. Filtration through silica gel yielded a colourless oil.
  • the mixture was subsequently warmed to ⁇ 20° C., and the orange solution was slowly added to an aqueous sodium hydrogensulfite/hydrogencarbonate solution.
  • the organic phase was separated and the aqueous phase was extracted with dichloromethane.
  • the combined organic phases were dried and the solvent was removed under reduced pressure.
  • the raw product was recrystallized twice from pentane at ⁇ 78° C.
  • the product was stirred in pentane in the presence of basic alumina and copper powder overnight, filtered through silica gel using pentane and crystallized from pentane at ⁇ 78° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Liquid Crystal Substances (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US10/220,428 2000-03-03 2001-03-02 Producing liquid crystals with CF2O bond Expired - Lifetime US6787062B2 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE10010537 2000-03-03
DE2000110537 DE10010537A1 (de) 2000-03-03 2000-03-03 Herstellung von Flüssigkristallen mit CF¶2¶O-Brücke
DE100-10-537.8 2000-03-03
DE100-27-102.2 2000-03-31
DE10027102 2000-05-31
DE10027102A DE10027102A1 (de) 2000-05-31 2000-05-31 Verfahren zur Herstellung von Flüssigkristallen mit CF¶2¶O-Brücke
PCT/EP2001/002402 WO2001064667A1 (fr) 2000-03-03 2001-03-02 Production de cristaux liquides avec ponts cf20

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US6787062B2 true US6787062B2 (en) 2004-09-07

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US (1) US6787062B2 (fr)
EP (1) EP1259503B1 (fr)
JP (2) JP4132818B2 (fr)
KR (1) KR100760562B1 (fr)
CN (1) CN100467460C (fr)
AT (1) ATE372996T1 (fr)
AU (1) AU2001246497A1 (fr)
DE (1) DE50113003D1 (fr)
HK (1) HK1054040A1 (fr)
TW (1) TW538117B (fr)
WO (1) WO2001064667A1 (fr)

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US20040054196A1 (en) * 2000-10-20 2004-03-18 Peer Kirsch Method for producing cyclic carboxylic orthoester fluorides and corresponding compounds
US20040059137A1 (en) * 2000-12-12 2004-03-25 Peer Kirsch Method for producing compounds having a cf2o bridge
US20150197471A1 (en) * 2013-04-05 2015-07-16 Dic Corporation Method for producing compound

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JP4972826B2 (ja) * 2001-04-10 2012-07-11 Ｊｎｃ株式会社 ジフルオロアルコキシを末端に有する化合物、液晶組成物および液晶表示素子
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EP1482018A1 (fr) 2003-05-27 2004-12-01 MERCK PATENT GmbH Aldéhydes avec un pont difluorooxyméthylène
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KR101577685B1 (ko) 2008-05-15 2015-12-15 제이엔씨 주식회사 광학적으로 등방성인 액정 매체 및 광 소자
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CN103058947B (zh) * 2012-12-24 2015-07-29 石家庄诚志永华显示材料有限公司 含有苯并噁唑和二氟亚甲氧基桥的液晶化合物及其制备方法与应用
CN103087038B (zh) * 2012-12-24 2015-07-29 石家庄诚志永华显示材料有限公司 含有苯并1,3-二氧杂环戊烷和二氟亚甲氧基桥的液晶化合物
CN103254903B (zh) * 2013-04-27 2016-04-06 石家庄诚志永华显示材料有限公司 含有二氟亚甲基键桥的液晶化合物及其制备方法与组合物
JP5975081B2 (ja) 2013-09-30 2016-08-23 ダイキン工業株式会社 含フッ素ビアリール化合物の製造方法
CN103787845A (zh) * 2014-01-21 2014-05-14 石家庄诚志永华显示材料有限公司 含有氘取代的二氟氧甲烷衍生物
CN106132915B (zh) 2014-03-20 2020-03-31 大金工业株式会社 具有氧二氟亚甲基骨架的化合物的制造方法
CN108251127A (zh) * 2014-11-20 2018-07-06 北京八亿时空液晶科技股份有限公司 一种含有二氟甲氧基桥键的液晶化合物及其应用
CN104560060A (zh) * 2014-12-16 2015-04-29 石家庄诚志永华显示材料有限公司 一种含氘代二氟甲氧桥类化合物的新型液晶介质及应用
CN104531167B (zh) * 2014-12-29 2017-02-22 石家庄诚志永华显示材料有限公司 液晶介质
CN115976648B (zh) * 2022-09-06 2024-09-27 中国科学院福建物质结构研究所 一种晶体材料及其制备方法和应用

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040054196A1 (en) * 2000-10-20 2004-03-18 Peer Kirsch Method for producing cyclic carboxylic orthoester fluorides and corresponding compounds
US6916940B2 (en) * 2000-10-20 2005-07-12 Merck Patent Gmbh Method for producing cyclic carboxylic orthoester fluorides and corresponding compounds
US20040059137A1 (en) * 2000-12-12 2004-03-25 Peer Kirsch Method for producing compounds having a cf2o bridge
US7105708B2 (en) * 2000-12-12 2006-09-12 Merck Patentgesellschaft Method for producing compounds having a CF2O bridge
US20060224023A1 (en) * 2000-12-12 2006-10-05 Peer Kirsch Process for the preparation of compounds having a CF2O bridge
US7385067B2 (en) 2000-12-12 2008-06-10 Merck Patent Gmbh Process for the preparation of compounds having a CF2O bridge
US20150197471A1 (en) * 2013-04-05 2015-07-16 Dic Corporation Method for producing compound
US9255055B2 (en) * 2013-04-05 2016-02-09 Dic Corporation Method for producing compound

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EP1259503A1 (fr) 2002-11-27
CN1411455A (zh) 2003-04-16
TW538117B (en) 2003-06-21
KR100760562B1 (ko) 2007-10-04
AU2001246497A1 (en) 2001-09-12
ATE372996T1 (de) 2007-09-15
EP1259503B1 (fr) 2007-09-12
CN100467460C (zh) 2009-03-11
US20030069433A1 (en) 2003-04-10
WO2001064667A1 (fr) 2001-09-07
HK1054040A1 (en) 2003-11-14
JP4132818B2 (ja) 2008-08-13
KR20030041857A (ko) 2003-05-27
JP2003525286A (ja) 2003-08-26
JP5037999B2 (ja) 2012-10-03
JP2007262069A (ja) 2007-10-11
DE50113003D1 (de) 2007-10-25

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